DFT Analysis of Dynamic, Charge, and TD-DFT Properties of Doped, Encapsulated, and Decorated First-Row Transition Metals on B12N12 Nanocage: Part 2.

Due to its distinctive properties and semiconducting characteristics, B12N12 has been the subject of many studies in the field of nanoscience, as it is a promising material for various applications, such as in electronics, catalysts, optoelectronic sensors and energy storage. In addition, the modification of B12N12 with transition metals (TM) increases its potential. Techniques such as charge decomposition analysis (CDA), UV–Vis spectroscopy, circular dichroism (CD), molecular dynamics (MD) and work function study (Φ) are applied in this work in order to investigate the dynamics of charge transfers, optical properties, chirality, electronic transitions and thermodynamic stability of pure and TM-modified B12N12. The calculations were developed at DFT-D3 and TD-DFT level with the B3LYP/6-31G(d,p) basis set. The CDA results showed that the charge transfer's predominant direction is from the cage to the TM, and that, in general, the charge donation effect is greater than the back-donation. The UV–Vis spectra analysis shows that pure B12N12 absorbs in the IR region, while modification with TM shifts the absorption peaks to the visible region in some cases. We observed that the presence of TM caused deformations in the structure of some nanocages, which began to show chirality as well as CD and g-factor signals. Molecular dynamics revealed that B12N12 and most of the modified nanocages are stable systems, but some changes in configuration were observed. The work function analysis indicated specific nanocages' potential in work function sensor applications. [ABSTRACT FROM AUTHOR]